CN106831555A - Pyridine amides and preparation method and application - Google Patents
Pyridine amides and preparation method and application Download PDFInfo
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- CN106831555A CN106831555A CN201710047155.4A CN201710047155A CN106831555A CN 106831555 A CN106831555 A CN 106831555A CN 201710047155 A CN201710047155 A CN 201710047155A CN 106831555 A CN106831555 A CN 106831555A
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- CIFZECKXXVHXOF-UHFFFAOYSA-N Cc1ccc(NC(OCc(cc2)ccc2[N+]([O-])=O)=O)nc1 Chemical compound Cc1ccc(NC(OCc(cc2)ccc2[N+]([O-])=O)=O)nc1 CIFZECKXXVHXOF-UHFFFAOYSA-N 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N O=C(CC1)OC1=O Chemical compound O=C(CC1)OC1=O RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- SOYWGEKUAUCEIX-UHFFFAOYSA-N O=C(Nc(cc1)ccc1OC(F)(F)F)Nc(cc1)ncc1Br Chemical compound O=C(Nc(cc1)ccc1OC(F)(F)F)Nc(cc1)ncc1Br SOYWGEKUAUCEIX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of pyridine amides and preparation method and application.The general structure of such compound is shown in formula I.Relevant biological activity verifies that find that there is some of which compound special brassinosteroid to react, such as the hypocotyl elongations of Arabidopsis Mutants det2 1 in promotion dark, rice leaf inclination increase strengthens ability of the resistance to salt stress of corn etc..Individual compound just has response very high in low concentration, and in addition in the case of high concentration, moreover it is possible to suppress the plant height of wheat, retarding of growing improves its ability resistant to lodging.There is good prevention effect on the grassy weeds such as control of wild oats, Triticum tauschii, barnyard grass, herba setariae viridis grass, goatweed simultaneously.Prepared by the series compound easy, and with low cost, agriculture application and popularization value is high, is worth follow-up further investigation exploitation.
Description
Technical field
The invention belongs to plant growth regulator field, it is related to a kind of pyridine amides and preparation method thereof and answers
With.
Background technology
Brassinosteroid, also known as brassin lactones (BRs), is the class endogenous plant growth regulating by synthesizing in plant
Agent.It can adjust plant various enzymes and hormone required in itself, give full play to plant itself potential and growth vigor, enhancing life
Life vigor and the waterlogging ability of drought resisting.In view of the content in plant such as brassin lactones is extremely low (to be less than 10-6) and it is used as plant ppm
The excellent physiologically active that thing hormone is shown in agricultural crops, its synthesis and transformation research are constantly subjected to scientists from all over the world
Favor.But and internal metabolism site with high costs for brassinosteroid synthesis be more, easily metabolic inactivation problem but beam
Hand finds new target drone acceptor and carries out the exploration of analog exploitation and increasingly cause people to pay close attention to without plan.
US6667278 (2003) is reported and has been copied first kind non-steroidal analog according to the structure and unit of BL, and is sieved
Choosing obtains high activity BM1 (pM grades), but high concentration (more than nM) is shown as without physiologically active, and must be cooperateed with IAA (5 μM)
Can play a role.
The content of the invention
It is an object of the invention to provide a kind of pyridine amides and preparation method and application.
The present invention provide pyridine amides, its general structure shown in formula I,
In the Formulas I, X=methyl or bromine；
Y=oxygen, imino group or methylene；
W=hydrogen, oxygen or sulphur；
R=propionyloxies, methyl propionate base, ethyl propionate base, ethyl sulfonic acid base, 2- methoxy ethyls, ethoxy carbonyl, 4- tri-
Fluorine methoxyphenyl, 4- nitrobenzyls or 2- hydroxyethyls.
Specifically, compound shown in the Formulas I is any one in following compound：
4- (5- picoline -2- amino) -4- ketobutyric acids,
4- (5- picoline -2- amino) -4- oxobutyrates,
4- (5- picoline -2- amino) -4- oxobutyrics,
3- (5- picoline -2- amino) -1- propane sulfonic acid,
2- methoxyethyls-N- (5- methyl -2- pyridines) carbamate,
[N- (5- methyl -2- pyridines) thioformamide] urethanes,
N- [4- Trifluoromethoxyphen-ls]-N- [5- methyl -2- pyridines] urea,
4- nitrobenzyls-N- (5- methyl -2- pyridines) carbamate,
3- (5- bromopyridine -2- amino) -1- propyl alcohol,
3- (5- bromopyridine -2- amino) -1- propane sulfonic acid,
[N- (5- bromo-2-pyridyls) thioformamide] urethanes or N- (4- Trifluoromethoxyphen-ls)-N- (5-
Bromo-2-pyridyl) urea.
The method of compound, comprises the following steps shown in the formula I that the present invention passes through：
Compound shown in Formula II and reactant III are carried out into acylation reaction, reaction is finished and obtains chemical combination shown in the Formulas I
Thing；
In the Formula II, the definition of X is identical with the definition in Formulas I；
The reactant III is
It is describedIn, R1ForZ is C or S；
It is describedIn, R2For
It is describedIn, the definition of W, Y and R is identical with the definition in Formulas I.
In the above method, in the acylation reaction step, compound shown in Formula II is 1 with the mol ratio of reactant III:
(0.9-1.2), concretely 1:1.1；
The reaction is carried out in a solvent；The solvent is chosen in particular from tetrahydrofuran, dichloromethane, ethyl acetate, acetone
With at least one in acetonitrile；
The reactant III isWhen, the acylation reaction is carried out in -5 DEG C -5 DEG C or room temperature；During reaction
Between be 3-4h；
The reactant III isWhen, the reaction temperature of the acylation reaction is the backflow of solvent for use
Temperature；Reaction time is 2-6h, concretely 2-3h；
The reactant III isWhen, the reaction temperature of the acylation reaction is room temperature；Instead
It is 3-12h between seasonable, concretely 5h.
Methods described also comprises the following steps：It is described after completion of the reaction, reaction system is purified；
The method of the purifying is specially recrystallization or solvent mashing；
In the re-crystallization step, solvent for use is specially ethanol or ethyl acetate；
In the solvent mashing step, solvent for use is specially ethanol or is 2 by volume ratio:1 ethyl acetate and oil
The mixed liquor of ether composition；
The solvent mashing step is specifically included：To mashing solvent for use is added in the reaction system, stir to product
Separate out, suction filtration；The reaction system is specially 1g with the amount ratio of solvent mashing step solvent for use：5mL.
In addition, the invention described above provide Formulas I described in compound coordinate plant growth activity in application and contain formula I
The plant growth active regulator of compound, falls within protection scope of the present invention.
Specifically, coordinate plant growth activity for it is following any one：
1) plant growth is promoted；
2) promote cane elongation and/or increase thick；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) plant lodging tolerance is strengthened；
7) anti-adversity of plant is strengthened；
The plant growth active regulator is at least one conditioning agent with following function：
1) plant growth is promoted
2) promote cane elongation and/or increase thick；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) plant lodging tolerance is strengthened；
7) anti-adversity of plant is strengthened；
The anti-adversity of the enhancing plant is specially the resistance to salt stress ability of enhancing plant；
The plant is specially paddy rice, corn or wheat.
In addition, application of the compound in weeding and the weeding containing type I compound described in the Formulas I of the invention described above offer
Agent, falls within protection scope of the present invention.
Specifically, the grass is grassy weed；Specially wild oat, Triticum tauschii, barnyard grass, herba setariae viridis grass or goatweed；
The formulation of the plant growth active regulator or herbicide is water dispersible granules, suspending agent, aqueous emulsion, tablet or microcapsules.
Carrier in above-mentioned formulation can be various common carriers, as long as ensureing that it is easy to after being prepared with compound shown in formula I
Pending site is applied to, for example, can be plant, seed or soil；Or be conducive to storing, transport or operating.Carry
Body can be solid or liquid, or usually gas but the material of boil down to liquid.
The compound of present invention design synthesis is the special picolinamide class brassinosteroid analogs of a class formation, is passed through
Relevant biological activity verifies that there is discovery some of which compound special brassinosteroid to react, and such as promotes plan south in dark
Mustard mutant det2-1 hypocotyl elongations, rice leaf inclination increase, strengthen ability of the resistance to salt stress of corn etc..Individual compound
Just there is response very high in low concentration, in addition in the case of high concentration, moreover it is possible to suppress the plant height of wheat, retarding of growing is carried
Its ability resistant to lodging high.Have on the grassy weeds such as control of wild oats, Triticum tauschii, barnyard grass, herba setariae viridis grass, goatweed simultaneously
There is good prevention effect.Prepared by the series compound easy, and with low cost, agriculture application and popularization value is high, is worth follow-up
Further investigation exploitation.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
State method and be conventional method unless otherwise instructed.The raw material can be obtained from open commercial sources unless otherwise instructed.
The preparation of embodiment 1, compound 1a：
Reaction scheme is shown below：
In 100mL round-bottomed flasks, 2- amino -5- picolines (10mmol) and succinic anhydride (12mmol) are added,
15mL tetrahydrofurans (solvent orange 2 A) stirring and dissolving, temperature rising reflux carries out acylation reaction for 2 hours, and reaction finishes cooling down precipitation
Solid, filters to obtain solid, ethyl alcohol recrystallization purifying.Recrystallizing specific method is：In to 1g head products to be recrystallized, it is added dropwise over
Ethanol 3mL, is heated to reflux, until head product all dissolves, continues the 10min that flows back, and rear slow cooling separates out solid, and suction filtration obtains pure
Net product.
The preparation of embodiment 2, compound 1c：
Reaction scheme is shown below：
In 100mL round-bottomed flasks bottle, 2- amino -5- picolines (10mmol), 3ml (20mmol) triethylamine are added,
15mL tetrahydrofuran stirring and dissolvings, ice salt bath is cooled to 0 DEG C, and constant temperature is added dropwise the 5ml tetrahydrochysene furans of produced monoesters succinyl chloride
Mutter solution, 20min completion of dropping；Ice bath is removed, room temperature is to slowly warm up to, continues acylation reaction 2-3 hours, reactant mixture
Pour into 150mL frozen water, ethyl acetate extracts (3x 100mL), saturated common salt water washing (3x 100mL), anhydrous Na 2SO4 does
Dry, filtering and concentrating, crude product is purified by ethanol or re-crystallizing in ethyl acetate.Recrystallizing specific method is：Wait to recrystallize to 1g
In head product, ethyl acetate 3mL is added dropwise over, be heated to reflux, until head product all dissolves, continue the 10min that flows back, afterwards slowly
Cooling separates out solid, and suction filtration obtains clean product.
The preparation of embodiment 3, compound 1g：
Reaction scheme is shown below：
In 100mL round-bottomed flasks, 2- amino -5- picolines (10mmol), 15ml tetrahydrofuran stirring and dissolvings are added,
Another to add 4- (trifluoromethoxy) phenyl isocyanate (10mmol), reactant mixture is stirred at room temperature carries out acylation reaction, TLC
Detection reaction process.After reaction terminates, a large amount of solids are separated out, be concentrated to give crude product, purified by ethyl alcohol recrystallization.Recrystallization tool
Body method is：In to 1g head products to be recrystallized, ethanol 3mL is added dropwise over, be heated to reflux, until head product all dissolves, after
Continuous backflow 10min, rear slow cooling separates out solid, and suction filtration obtains clean product.
According to upper identical method, the compound of listed remaining the ownership Formulas I of table 1 can be prepared.
The structure and yield of compound 1a-1l are as shown in table 1 below：
Table 1, the molecular formula of synthesis compound (1a-1l) and yield
The growth regulating-activity of embodiment 4, plant is determined
Arabidopsis Mutants det2-1 seeds with 70% ethanol disinfection 1min, while 1% sodium hypochlorite 15min, sterilized water
Clean and be seeded in 1/2MS (compound of 0.8% agar, 1% sucrose and prescribed concentration)；4 DEG C of refrigerator vernalization 3 days, then transfer
To dark condition, 22 DEG C are cultivated 7 days, and after whole strain is taken pictures, ImageJ softwares measure its hypocotyl length.
Result of the test
All compound test results are as Table 2,3
Table 2, comparison medicament Hypocotyls Elongation of Arabidopsis measurement result
In table 2,24-epiBL is 24- epi-brassinolides；CAS is 78821-43-9；The CAS of Bikinin is 188011-
69-0。
Table 3, Hypocotyls Elongation of Arabidopsis measurement result
From above-mentioned table 2,3 as can be seen that 24-epiBL has activity very high, in 1 μM of concentration, hypocotyl length reaches
0.9413 ± 0.0748cm, and the non-steroidal brassinosteroid analogs Bikinin for having reported extends activity and is better than at 40 μM
24-epiBL, reaches 1.1086 ± 0.0684cm；In the compound of all design synthesis, 1c is to Arabidopsis Mutants hypocotyl
With elongation activity very high, maximum reaches 0.8028 ± 0.0725cm；Meanwhile, have under 1j, 1k high concentration and suppress lower embryo
The activity of elongate axis, minimum value reaches 0.1641 ± 0.0181cm.Because compound is with low cost, under square one, have
Value very high.
Embodiment 5, Rice laminae inclination is tested
Paddy rice (Nipponbare) seed 10%H2O2Sterilization 20min, sterilized water is cleaned, and is sprouted 3 days in 30 DEG C of incubators, children
Bud illumination cultivation 5-6 days, intercepts during Leaf inclination position is placed in the liquid of various concentrations under 28 DEG C of dark conditions and places 48h, measures
Angle device measurement Leaf inclination.
All compound test results are as shown in table 4,5
The rice leaf inclination measurement result of table 4
Table 5 synthesizes compound rice leaf inclination measurement result
From the above, it can be seen that 24-epiBL has activity very high, in 10 μM of concentration, blade pitch angle reaches 125
± 9 °, and Bikinin is in 100 μM of Cmax, activity is not so good as 24-epiBL, can only achieve 75 ± 8 °；Closed in all designs
Into compound in, 1c, 1d have activity very high to blade lean, and maximum reaches 53 ± 7 °, and 1k inclines to blade in addition
Tiltedly there is the effect for suppressing increase, minimum value reaches 13 ± 3 ° of performances of reactive compound with Hypocotyls Elongation of Arabidopsis experiment one
Cause, show that compound has brassinosteroid related activity, while design compound is with low cost, under square one, have
Value very high.
Embodiment 6, compound controls growth test to wheat seedling
Wheat (winter wheat Jimai 22) seed is cleaned and is seeded in 0.8% with 10% dioxygen water sterilization 15-20min, sterilized water
The compound of agar and prescribed concentration), 25 DEG C of incubator dark germination 2 days, under subsequent 100% illumination, 65% damp condition, 26
DEG C culture 6 days, measure wheat plant height, statistic analysis result.
Statistical experiment result is as shown in table 6,7：
Influence of the comparison medicament of table 6 to Plant Height in Wheat
Table 7 synthesizes influence of the compound to Plant Height in Wheat
From the data in table 6,7 it is known that some compounds prepared by the present invention have to wheat seedling retarding of growing
Good effect, such as 1c, 1d, 1k；Wherein 1k controls plant height minimum value reaches 3.04 ± 0.21cm, similar to Bikinin；Simultaneously
The normal growth development of plant is not contained.In the extreme circumstances, these effects help to prevent the lodging of wheat from occurring, and ensure small
Wheat stable yields and normal economic benefit.
Influence experiment of the embodiment 7, compound to Maize Seedling Under Salt Stress biomass
Selection full seed, in the same size, nothing are gone mouldy, the corn seed (Zheng Dan 958) of no disease and pests harm, with control 24-
EpiBL (1.0mg/L), Bikinin (40mg/L) and medicament to be measured (40mg/L) normal temperature seed soaking 24h, after the completion of seed soaking, with sterilizing
Filter paper suck dry moisture is standby.The seed of seed soaking is placed in the germination box for being covered with quartz sand, add 150mM in every box
NaCl solution 10mL, the vernalization at 28 DEG C in incubator, per 25, box, if 3 repetitions, (CK) is processed as control with clear water,
(daytime is cultivated in illumination box：18h, 26 DEG C；100% illumination, night：6h, 20 DEG C).Treatment fluid is changed daily, and germination is extremely
At the 8th day, 10 plants of biomass of seedling of random measurement (weigh seedling fresh weight, after be placed in 48h dried in 80 DEG C of baking ovens, weigh dry weight
Amount).
Experimental result is as shown in chart 8：
The influence of the comparison medicament of table 8 and compound to corn seedling biomass
From the data in table 8 it is known that some compounds of present invention preparation are to the biology under corn seedling salt stress
Amount accumulation has certain effect, and wherein 1c, 1d performance is excellent, actual similar to Bikinin significantly beyond clear water control, together
When promote stress under germination.However, 1k but shows abnormal inhibition, fresh weight and dry weight are reduced.In severe feelings
Under condition, these effects assist in normal growth and the development of slight maize under NaCl stress, ensure the normal economic effect of corn
Benefit.
Embodiment 8, compound is tested weed seed Inhibiting germination
The liquid of the 80mg/L being configured to 1c, 1d, 1k is carried out to weeds (wild oat, herba setariae viridis grass, goatweed) seed
Culture dish is soaked seed 24h, and sterilized water is cleaned and is seeded in bottom and is lined with the 6cm batch cultur wares of two layers of filter paper, uniformly put per ware
Big full and uniform 20, the seed of appropriate grain is put, 3 repetitions process (CK) as control, trained during experiment with clear water
Support ware filter paper and be always maintained at moistening.Dark culturing (daytime in incubator：18h, 25 DEG C；Night：6h, 20 DEG C), count 3 days and germinate
Gesture and 7 days germination percentages.
Experimental result is as shown in table 9：
Inhibiting germination activity of the compound of table 9 to weeds
From the results shown in Table 9, under the high drug concentration of 80mg/L, herba setariae viridis grass, goatweed and wild oat
Germination is all subject to a certain degree of suppression.In herba setariae viridis grass, suppress most preferably 1k, inhibiting rate has reached 51%；Its
Secondary is 1c, has reached 22.8%.In goatweed, suppress best still 1k, inhibiting rate has reached 40.3%；Next to that 1c, reaches
To 24.6%.Suppression of the 1k to wild oat is also best, has reached 53.3%；Next to that 1c, has reached 20.8%；
1d also has 13.9% inhibiting rate.With the raising of concentration, drug effect may be more preferable, and wherein 1k has application value very high,
It is worth follow-up developmental research.
The preparation of embodiment 9, compound 1a water dispersible granules (10%)
1a 10g, wetting dispersing agent fatty alcohol sulfate salt 6g, disintegrant ammonium sulfate 3g, carrier kaolin is weighed to complement to
100g, is sufficiently mixed uniform, and wettable powder is ground into through airslide disintegrating mill, in adding fluidized bed drying comminutor, with containing
The aqueous solution of adhesive polyethylene glycol 2g, in the fluidized bed prilling of (50 DEG C -70 DEG C), dries in drying machine, is obtained after screening
10%1a water dispersible granules products.
The water dispersible granules of other general formula compounds can be prepared by the above method.
The preparation of embodiment 10, compound 1b aqueous suspension agents (25%)
Weigh 1b 25g, emulsifying agent NPEPO44.8g, desugar lignosulfonates 1.2g, together with adding water, total amount 70g is added
Barreling is carried out in sand milling kettle, after 1h, thickener xanthans 0.15g, antifreeze glycol 4g and remaining water 100% is supplied,
In addition system, it is modulated, obtains the homogeneous aqueous suspension agent of 1b (25%) whites.
The aqueous suspension agent of other general formula compounds can be prepared by the above method.
The preparation of embodiment 11, compound 1c aqueous emulsions (5%)
Weigh 1c 5g and emulsifying agent agriculture breast 501#2.8g, co-emulsifier agriculture breast 601#7.2g is added together, and makes to be dissolved into
Even oil phase.Water, antifreeze ethylene glycol 5g are mixed, as homogeneous water phase.Under normal temperature and high-shear emulsion machine stirring,
Water is added to oil phase, well dispersed aqueous emulsion is formed.
The aqueous emulsion of other general formula compounds can be prepared by the above method.
The preparation of embodiment 12, compound 1d effervescent tablets (1%)
Weigh after 1d 1g are dried 24 hours at 80 DEG C and pack, oxalic acid 30g, sodium acid carbonate 30g mechanical crushings are arrived
100 mesh, diatomite 0.1g, lactose 3g, white carbon 31g and talcum powder 5g mixing and stirrings, are crushed to 800 mesh, with 1d mixed
Close mixer in stirring 10 minutes after be pressed into effervescent tablet, pack product.
The tablet of other general formula compounds can be prepared by the above method.
Embodiment 13, the 20 μm of preparations of microcapsules (3%) of compound 1e particle diameters
Weigh 2.0g shitosans and 1.0g gelatin is dissolved in the acetum of 100ml 2%, by 2ml Sorbitans acid potassium list
Laurate is slowly added into above-mentioned solution under 800rpm stirrings, persistently stirs 20min.Again by 1.0ml fatty alcohol polyoxies
Vinethene mixes with 2.0ml 7.5%1e ethanol solutions, stirring and emulsifying 10min under 1000rpm.Then, the emulsion of 1e is existed
It is slowly added into the acetum of the shitosan and gelatin for having emulsified under 1200rpm stirrings, continues to stir 45min until mixed
Close liquid dispersed.Finally by obtained mixed liquor in the spray dryer that inlet temperature is 135 DEG C, outlet temperature is 85 DEG C
Solidification drying is carried out, gained powder is 1e slow-release microcapsules.After measured, medicine encystation rate 83%, carrying drug ratio 3.0%, averagely
20.5 μm of particle diameter.
The microcapsules of other general formula compounds can be prepared by the above method.
The influence (Hypocotyls Elongation of Arabidopsis experiment) of embodiment 14, different 1c compound formulations to drug effect
Arabidopsis Mutants det2-1 seeds with 70% ethanol disinfection 1min, while 1% sodium hypochlorite 15min, sterilized water
Clean and be seeded in 1/2MS (0.8% agar, 1% sucrose and certain density 1c compound formulations)；4 DEG C of refrigerator vernalization 3 days, with
After be transferred under dark condition, 22 DEG C cultivate 7 days, after whole strain is taken pictures, ImageJ softwares measure its hypocotyl length.Formulation concentrations
It is 0.02mg/g (20mg/L) that compound method is, by the concentration indicated, to add water the preparation of various concentration or DMSO is diluted to institute
The concentration for needing.
Result of the test
All compound test results are as shown in table 10.
The Hypocotyls Elongation of Arabidopsis measurement result of table 10
From the data in table 10 it is known that the 1c compound formulations that prepare of the present invention to the drug effect of arabidopsis hypocotyl all
It is better than the treatment of pure medicament.Wherein water dispersible granules, aqueous suspension agent, aqueous emulsion and microcapsules are demonstrated by activity higher,
It is better than tablet and 1g under the concentration of 20mg/L, has highlighted most of commercial formulation to improving the effect of drug effect.For the later stage
Application study provides certain directive significance.
Attached all compound spectral characterization data
4- (5- picoline -2- amino) -4- ketobutyric acids (1a)
1H NMR(300MHz,CDCl3- d) δ 10.95 (s, 1H), 8.27 (d, J=8.6Hz, 1H), 7.93 (dt, J=2.5,
0.8Hz, 1H), 7.62 (ddd, J=8.6,2.4,0.8Hz, 1H), 2.85 (d, J=2.1Hz, 4H), 2.31 (s, 3H)13C
NMR(75MHz,DMSO-d6)δ174.05,170.96,154.39,147.68,138.47,120.49,113.01,31.13,
29.01,17.34.HRMS m/z:209.0918(M+H+,calcd for C7H8N2O3S,209.0921)mp:170.7-172.5
℃
4- (5- picoline -2- amino) -4- oxobutyrates (1b)
1H NMR(300MHz,CDCl3- d) δ 10.44 (s, 1H), 8.13 (dq, J=2.2,0.7Hz, 1H), 7.95 (d, J=
8.4Hz, 1H), 7.57 (dd, J=8.6,2.4Hz, 1H), 3.59 (s, 2H), 2.73-2.45 (m, 4H), 2.23 (s, 3H)13C
NMR(75MHz,DMSO-d6)δ172.90,170.56,150.00,147.67,138.46,128.07,113.02,51.40,
30.79,28.43,17.31.HRMS m/z:223.1080(M+H+,calcd for C7H8N2O3S,223.1077)mp:124.1-
125.1℃
4- (5- picoline -2- amino) -4- oxobutyrics (1c)
1HNMR(300MHz,CDCl3- d) δ 10.47 (s, 1H), 8.13 (dd, J=2.1,1.1Hz, 1H), 7.94 (d, J=
8.5Hz, 1H), 7.59 (dd, J=8.6,2.4Hz, 1H), 4.05 (q, J=7.1Hz, 2H), 2.72-2.45 (m, 5H), 2.24
(s, 2H), 1.17 (t, J=7.1Hz, 3H)13C NMR(75MHz,DMSO-d6)δ172.37,170.66,149.91,147.42,
138.65,128.09,113.07,59.95,30.82,28.66,17.30,14.14.HRMS m/z:237.1232(M+H+,
calcd for C7H8N2O3S,237.1234)mp:87.4-89.1℃
3- (5- picoline -2- amino) -1- propane sulfonic acid (1d)
1H NMR(300MHz,D2O) δ 7.67-7.46 (m, 2H), 6.89 (d, J=9.0Hz, 1H), 4.23-4.11 (m,
2H), 2.89 (t, J=7.3Hz, 2H), 2.25-2.06 (m, 5H)13C NMR(75MHz,DMSO-d6)δ151.83,144.55,
136.65,124.14,114.55,46.74,22.26,15.77.
HRMS m/z:231.0798(M+H+,calcd for C7H8N2O3S,231.0798)mp:314.3-315.5℃
2- methoxyethyls-N- (5- methyl -2- pyridines) carbamate (1e)
1H NMR(300MHz,DMSO-d6) δ 10.05 (s, 1H), 8.09 (dt, J=2.5,0.8Hz, 1H), 7.76-7.65
(m, 1H), 7.57 (dd, J=8.4,2.3Hz, 1H), 4.26-4.15 (m, 2H), 3.61-3.50 (m, 2H), 3.28 (s, 3H),
2.22(s,3H).13C NMR(75MHz,DMSO-d6)δ153.63,150.09,147.65,138.68,127.50,112.03,
70.18,63.57,58.13,17.25.
HRMS m/z:211.1077(M+H+,calcd for C7H8N2O3S,211.1077)mp:110.1-111.7℃
[N- (5- methyl -2- pyridines) thioformamide] urethanes (1f)
1H NMR(300MHz,CDCl3-d)δ12.09(s,1H),11.46(s,1H),8.57(s,1H),8.27–8.17(m,
1H), 7.71 (dd, J=8.5,2.4Hz, 1H), 4.22 (q, J=7.1Hz, 2H), 2.29 (s, 3H), 1.26 (t, J=7.1Hz,
3H).13C NMR(75MHz,DMSO-d6)δ177.24,153.45,149.23,148.05,138.43,130.43,115.04,
62.26,17.43,14.18.HRMS m/z:240.0799(M+H+,calcd for C7H8N2O3S,240.0801)mp:115.2-
117.0℃
N- [4- Trifluoromethoxyphen-ls]-N- [5- methyl -2- pyridines] urea (1g)
1H NMR(300MHz,DMSO-d6) δ 10.61 (s, 1H), 9.40 (s, 1H), 8.12 (dd, J=2.4,1.1Hz,
1H), (s, the 3H) of 7.69-7.54 (m, 3H), 7.41 (d, J=8.5Hz, 1H), 7.37-7.27 (m, 2H), 2.2313C NMR
(75MHz,DMSO-d6)δ153.32,149.88,147.76,147.17,144.68,138.68,130.98–121.02(m),
112.05,17.27.HRMS m/z:312.0957(M+H+,calcd for C7H8N2O3S,312.0954)mp:184.5-186.0
℃
4- nitrobenzyls-N- (5- methyl -2- pyridines) carbamate (1h)
1H NMR(300MHz,DMSO-d6) δ 10.31 (s, 1H), 8.33-8.20 (m, 2H), 8.11 (d, J=2.2Hz,
1H), (s, the 3H) of 7.70 (t, J=8.1Hz, 3H), 7.59 (dd, J=8.5,2.4Hz, 1H), 5.32 (s, 2H), 2.2313C NMR
(75MHz,DMSO-d6)δ152.33,150.75,146.46,143.12,139.22,138.52,126.49,121.99,
121.78,120.06,111.66,17.18.
HRMS m/z:288.0980(M+H+,calcd for C7H8N2O3S,288.0979)mp:179.6-181.6℃
3- (5- bromopyridine -2- amino) -1- propyl alcohol (1i)
1HNMR(300MHz,DMSO-d6) δ 8.00 (dd, J=2.6,0.6Hz, 1H), 7.48 (dd, J=8.9,2.6Hz,
1H), 6.74 (t, J=5.5Hz, 1H), 6.44 (dd, J=9.0,0.7Hz, 1H), 3.46 (td, J=6.3,5.2Hz, 2H),
3.23 (td, J=7.0,5.6Hz, 2H), 1.65 (p, J=6.6Hz, 2H)13C NMR(75MHz,DMSO-d6)δ157.82,
147.75,138.81,110.16,104.75,58.72,38.08,32.27.HRMS m/z:231.0126(M+H+,calcd
for C7H8N2O3S,231.0128)mp:83.1-83.8℃
3- (5- bromopyridine -2- amino) -1- propane sulfonic acid (1j)
1HNMR(300MHz,D2O) δ 8.05 (d, J=2.1Hz, 1H), 7.82 (dd, J=9.5,2.2Hz, 1H), 6.93 (d,
J=9.5Hz, 1H), 4.26-4.14 (m, 2H), 2.91 (t, J=7.2Hz, 2H), 2.26-2.08 (m, 2H)13CNMR(75MHz,
DMSO-d6)δ166.51,153.11,144.41,138.68,116.64,46.72,22.06.HRMS m/z:294.9748(M+H+,calcd for C7H8N2O3S,294.9747)mp:232.4-234.1℃
[N- (5- bromo-2-pyridyls) thioformamide] urethanes (1k)
1HNMR(300MHz,CDCl3- d) δ 11.73 (s, 1H), 8.62 (s, 1H), 8.54 (dd, J=2.5,0.7Hz, 1H),
(t, J=7.1Hz, the 3H) of 8.13 (dd, J=8.9,2.5Hz, 1H), 4.23 (q, J=7.1Hz, 2H), 1.2713CNMR(75MHz,
DMSO-d6)δ177.53,153.52,150.25,148.89,140.53,116.91,115.52,62.45,14.18.HRMS m/
z:303.9748(M+H+,calcd for C7H8N2O3S,303.9750)mp:139.4-141.4℃
N- (4- Trifluoromethoxyphen-ls)-N- (5- bromo-2-pyridyls) urea (1l)
1H NMR(300 MHz,DMSO-d6) δ 9.98 (s, 1H), 9.52 (s, 1H), 8.40 (dd, J=2.6,0.6 Hz,
1H), (m, 2H) of 7.98 (dd, J=8.9,2.5 Hz, 1H), 7.71-7.55 (m, 3H), 7.38-7.2713C NMR(75MHz,
DMSO-d6) δ 151.81 (d, J=16.4 Hz), 147.79,143.26,140.79,138.24,120.90 (d, J=127.4
), Hz 112.80 (d, J=149.5 Hz) .HRMS m/z:375.9902(M+H+,calcd for C7H8N2O3S,375.9903)
mp:210.4-212.2℃。
Claims (10)
1. compound shown in Formulas I,
In the Formulas I, X=methyl or bromine；
Y=oxygen, imino group or methylene；
W=hydrogen, oxygen or sulphur；
R=propionyloxies, methyl propionate base, ethyl propionate base, ethyl sulfonic acid base, 2- methoxy ethyls, ethoxy carbonyl, 4- fluoroforms
Phenyl, 4- nitrobenzyls or 2- hydroxyethyls.
2. compound according to claim 1, it is characterised in that：During compound shown in the Formulas I is following compound
Any one：
4- (5- picoline -2- amino) -4- ketobutyric acids,
4- (5- picoline -2- amino) -4- oxobutyrates,
4- (5- picoline -2- amino) -4- oxobutyrics,
3- (5- picoline -2- amino) -1- propane sulfonic acid,
2- methoxyethyls-N- (5- methyl -2- pyridines) carbamate,
[N- (5- methyl -2- pyridines) thioformamide] urethanes,
N- [4- Trifluoromethoxyphen-ls]-N- [5- methyl -2- pyridines] urea,
4- nitrobenzyls-N- (5- methyl -2- pyridines) carbamate,
3- (5- bromopyridine -2- amino) -1- propyl alcohol,
3- (5- bromopyridine -2- amino) -1- propane sulfonic acid,
[N- (5- bromo-2-pyridyls) thioformamide] urethanes or N- (4- Trifluoromethoxyphen-ls)-N- (the bromo- 2- of 5-
Pyridine) urea.
3. a kind of method for preparing compound shown in Formulas I described in claim 1 or 2, comprises the following steps：
Compound shown in Formula II and reactant III are carried out into acylation reaction, reaction is finished and obtains compound shown in the Formulas I；
In the Formula II, the definition of X is identical with claim 1；
The reactant III is
It is describedIn, R1ForZ is C or S；
It is describedIn, R2For
It is describedIn, the definition of W, Y and R is identical with the definition in claim 1.
4. method according to claim 3, it is characterised in that：In the acylation reaction step, compound shown in Formula II
It is 1 with the mol ratio of reactant III:(0.9-1.2) or 1:1.1；
The reaction is carried out in a solvent；The solvent is chosen in particular from tetrahydrofuran, dichloromethane, ethyl acetate, acetone and second
At least one in nitrile；
The reactant III isWhen, the acylation reaction is carried out in -5 DEG C -5 DEG C or room temperature；Reaction time is
3-4h；
The reactant III isWhen, the reaction temperature of the acylation reaction is the reflux temperature of solvent for use；
Reaction time is 2-6h or 2-3h；
The reactant III isWhen, the reaction temperature of the acylation reaction is room temperature；During reaction
Between be 3-12h or 5h.
5. the method according to claim 3 or 4, it is characterised in that：Methods described also comprises the following steps：In the reaction
After finishing, reaction system is purified；
The method of the purifying is specially recrystallization or solvent mashing；
In the re-crystallization step, solvent for use is specially ethanol or ethyl acetate；
In the solvent mashing step, solvent for use is specially ethanol or is 2 by volume ratio:1 ethyl acetate and petroleum ether group
Into mixed liquor；
The solvent mashing step is specifically included：To mashing solvent for use is added in the reaction system, stirring to product is separated out,
Suction filtration；The reaction system is specially 1g with the amount ratio of solvent mashing step solvent for use：5mL.
6. application of the compound described in Formulas I described in claim 1 or 2 in coordinate plant growth activity；
Plant growth active regulator containing any type I compound in claim 1-2.
It is 7. according to claim 6 to apply or plant growth active regulator, it is characterised in that：The coordinate plant growth
Activity for it is following any one：
1) plant growth is promoted；
2) promote cane elongation and/or increase thick；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) plant lodging tolerance is strengthened；
7) anti-adversity of plant is strengthened；
The plant growth active regulator is at least one conditioning agent with following function：
1) plant growth is promoted；
2) promote cane elongation and/or increase thick；
3) seed germination rate is improved；
4) yield is improved；
5) improving quality；
6) plant lodging tolerance is strengthened；
7) anti-adversity of plant is strengthened；
The anti-adversity of the enhancing plant is specially the resistance to salt stress ability of enhancing plant；
The plant is specially paddy rice, corn or wheat.
8. application of the compound in weeding described in Formulas I described in claim 1 or 2；
Herbicide containing any type I compound in claim 1-2.
9. application according to claim 8 or herbicide, it is characterised in that：The grass is grassy weed；It is specially wild
Oat, Triticum tauschii, barnyard grass, herba setariae viridis grass or goatweed.
10., according to any described application or plant growth active regulator or herbicide in claim 6-8, its feature exists
In：The formulation of the plant growth active regulator or herbicide is water dispersible granules, suspending agent, aqueous emulsion, tablet or micro- glue
Capsule.
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